EP0088527B1 - Promoteurs d'adhésion - Google Patents

Promoteurs d'adhésion Download PDF

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Publication number
EP0088527B1
EP0088527B1 EP83300754A EP83300754A EP0088527B1 EP 0088527 B1 EP0088527 B1 EP 0088527B1 EP 83300754 A EP83300754 A EP 83300754A EP 83300754 A EP83300754 A EP 83300754A EP 0088527 B1 EP0088527 B1 EP 0088527B1
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EP
European Patent Office
Prior art keywords
monophosphate
polyethylenically unsaturated
adhesion
composite
phosphate
Prior art date
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Expired
Application number
EP83300754A
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German (de)
English (en)
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EP0088527A3 (en
EP0088527A2 (fr
Inventor
Richard William Billington
Gordon Brian Blackwell
Terence Ernest Prodger
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Dentsply Research and Development Corp
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Dentsply Research and Development Corp
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Application filed by Dentsply Research and Development Corp filed Critical Dentsply Research and Development Corp
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Publication of EP0088527A3 publication Critical patent/EP0088527A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Definitions

  • This invention is concerned with improvements in and relating to adhesion promotors, especially for use in promoting the adhesion of addition polymerizable dental materials to natural teeth.
  • Addition polymerizable dental materials such as filling materials, cements and the like, generally comprise a mixture of a finely divided inert filler with one or more ethylenically unsaturated materials capable of in situ polymerization in a dental cavity to form a hard filling material.
  • a finely divided inert filler with one or more ethylenically unsaturated materials capable of in situ polymerization in a dental cavity to form a hard filling material.
  • a wide variety of fillers may be employed and examples thereof include finely divided glasses, ceramics and inorganic oxides containing e.g. silicon and aluminium.
  • the filler will generally have been subjected to an appropriate surface treatment such as silanation or with a titanate.
  • the finely divided inert filler may form less than 50% by weight of the composite material, but commonly forms from 50 to 85% by weight thereof and especially from 60 to 80% by weight thereof.
  • the inert filler suitably has an average particle size of from 1 to 100, preferably from 1 to 60 pm.
  • a filler may be replaced by, or used in admixture with a superfine filler, e.g. having a particle size of from 10 to 400 nm as disclosed in British Patent Specification No. 1,488,403, in which case the filling material may contain lower amount, e.g. 30-50% by weight, of filler.
  • Other addition polymerizable dental materials comprise a mixture of an organic filler, e.g. a polymer or copolymer of methyl methacrylate, together with an ethylenically unsaturated material, typically methyl methacrylate.
  • an organic filler e.g. a polymer or copolymer of methyl methacrylate
  • the ethylenically unsaturated component or binder of the composite material generally comprises one or more esters of ethylenically unsaturated carboxylic acids, especially of acrylic or methacrylic acid.
  • the ethylenically unsaturated binder component may comprise simple esters of unsaturated carboxylic acids with monohydric aliphatic alcohols, for example methyl (meth)acrylate, ethyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.
  • (meth)acrylate is intended to refer to an acrylic or methacrylic acid ester of a hydroxyl group-containing compound).
  • the unsaturated component may comprise unsaturated carboxylic esters of polyhydric alcohol, especially polyhydric alcohols containing one or more phenyl groups, such as the adduct of bisphenol A and glycidyl methacrylate, Bisphenol A (meth)acrylate and/or reaction products of 2-hydroxyethyl (meth)acrylate with isophthalic, terephthalic or phthalic acid chloride.
  • Another class of ethylenically unsaturated binder comprises the adducts, of Bis-GMA and an isocyanate or diisocyanate as described in U.S. Patent No. 3,629,187.
  • monoesters of dihydric alcohols e.g. ethylene glycol mono(meth)acrylate
  • polyisocyanates especially aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate or hexamethylene diisocyanate.
  • aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate or hexamethylene diisocyanate.
  • the unsaturated component may also comprise an unsaturated flourine-containing material, as disclosed for example in United States Patent No. 4292029, which additionally serves to reduce penetration of fluids between tooth surfaces and restorative material.
  • the composite materials should also contain, when filled into a tooth cavity, a polymerisation initiator for effecting polymerisation of the ethylenically unsaturated binder component.
  • a polymerisation initiator for effecting polymerisation of the ethylenically unsaturated binder component.
  • Such initiator should, of course, be capable of initiating polymerisation at comparatively low temperatures, i.e. mouth temperatures, and examples of suitable initiators include organic peroxides, such as benzoyl peroxide or tert.butyl peroctanoate, desirably together with an activator e.g. a tertiary amine activator such as N,N-dimethyl-p-toluidine, or ascorbic or sulphinic acid or a salt thereof.
  • an activator e.g. a tertiary amine activator such as N,N-dimethyl-p-toluidine, or ascorbic or sulphinic acid or
  • the composite filling material may contain an initiator sensitive to visible or ultraviolet light which, on exposure to such light, initiates polymerisation of the ethylenically unsaturated binder component.
  • initiators include chlorobenzophenone and benzoin methyl ether (for U.V. light) and camphorquinone (for visible light).
  • an accelerator such as a secondary or teritary amine, may also be employed in order to accelerate the reaction.
  • EP-A-0 017 937 discloses bonding compositions for hard tissue of the human body comprising, as the main components, at least one polymerisable monomer selected from acrylate esters, methacrylate esters, acrylamide derivatives and methacrylamide derivatives wherein all the members of said monomer group contain a carboxyl, epoxy, amino, phosphono or hydroxy group in the molecule and at least one alkoxy-containing titanium compound or alkoxy-containing titanium compound.
  • the adhesion of a composite material, as described above, to tooth enamel may be markedly improved by firstly applying to the tooth enamel a compound comprising a monophosphate radical (that is a group of the formula and at least three ethylenically unsaturated groups.
  • the composite filling material is then introduced into the cavity and cured therein, with concommitant polymerisation of the polyunsaturated phosphate.
  • the adhesion of the set composite filling material to the enamel is markedly improved, as compared with a comparable process wherein no polyunsaturated phosphate is employed, and there may be achieved degrees of adhesion comparable to those obtained with prior acid etching of the enamel.
  • an adhesion promoting composition suitable for improving the adhesion of a composite dental filling material to natural teeth comprising a solution, in a volatile organic solvent therefor, of an ethylenically unsaturated monophosphate of the formula I as hereinafter defined or salt thereof.
  • Suitable volatile organic solvents for use in the compositions of the invention include lower aliphatic alcohols, especially ethanol, and the concentration of the ethylenically unsaturated monophosphate in the solution is suitably from 0.5 to 10%, preferably from 0.5 to 2.5%, especially about 1%, by weight.
  • the polyethylenically unsaturated monophosphate for use in accordance with the invention may be represented by the formula: in which
  • Such compounds include pentaerythritol tri(meth)acrylate monophosphate and dipentaerythritol penta(meth)acrylate monophosphate.
  • the compounds of formula (I) are in themselves new compounds and are provided as a further feature of the invention.
  • the compounds of formula (I), may also be used in the form of their salts, for example alkali metal (e.g. sodium or potassium) or ammonium salts.
  • alkali metal e.g. sodium or potassium
  • Polyethylenically unsaturated monophosphates of formula (I) may be prepared by phosphorylating, (e.g. by reaction with phosphorous oxychloride or phosphorus pentoxide) a corresponding monohydroxy compound of the formula: in which R, R 1 and n have the meanings defined above.
  • adhesion may be enhanced by the use of an intermediate bonding resin, e.g. a polymerisable ethylenically unsaturated material containing little or no filler.
  • an intermediate bonding resin e.g. a polymerisable ethylenically unsaturated material containing little or no filler.
  • the solution of polyunsaturated phosphate is first applied to the tooth followed by a layer of intermediate bonding resin and finally the filling material is introduced.
  • the intermediate bonding resin may be used before or together with the curing of the filling material.
  • adhesion promotors of the invention may be used to improve the adhesion of fissure sealants which are material of similar composition to the intermediate bonding resins noted above.
  • the polyunsaturated phosphates may be employed to improve adhesion between a composite dental filling material and tooth enamel by first applying a composition containing the polyunsaturated phosphate to the tooth enamel and subsequently filling the cavity in the tooth with the filling material.
  • the polyunsaturated phosphate may be incorporated in the filling composition itself and, accordingly, another embodiment of the invention provides a composite dental filling material comprising (i) an inert finely divided filler; (ii) an ethylenically unsaturated binder material; (iii) an initiator for the ethylenically unsaturated binder; and (iv) a polyunsaturated phosphate of the formula I as defined above.
  • the proportions and contents of the filler, binder and initiator will be generally conventional and the polyunsaturated phosphate is suitably present in an amount of 1 to 20, preferably from 2 to 5% by weight, based on the total weight of the composite filling. It may be noted that, when present in a composite filling material, the polyunsaturated phosphate may also serve to promote adhesion between the inert filler and the binder, whereby to increase the strength of the cured material. In order to further improve this property the polyunsaturated phosphate may be coated onto the inert filler before compounding it with the remainder of the ingredients of the composite filling material.
  • the initiator system when the initiator system contains an amine the polyunsaturated phosphate may react or interfere therewith, thereby reducing the effectiveness of the initiator system. Accordingly, it is generally preferred that the initiator system does not contain an amine. However, this is not the case when the polyunsaturated phosphate is first applied to tooth material to act as an adhesion promotor as discussed above.
  • the catalyst or initiator be brought into contact with the polymerizable ingredient of the filling material only immediately before introduction of the filling material into a dental cavity.
  • the materials are intended to be polymerized by light or ultraviolet radiation, the material may be put up a single pack.
  • the adhesion promoting compositions of the invention may also be used to improve the adhesion to tooth enamel, of orthodontic appliances when using as adhesives a composite material or a polymerizable composition comprising one or more unsaturated materials such as are used as binders in composite filling materials.
  • the polyunsaturated phosphate may be used as an adhesion promoter for the treatment of enamel to which orthodontic brackets or bands are to be attached or, in periodontics, for the treatment of enamel to which a splint is to be attached.
  • they may be used as adhesion promotors in the build up of teeth with composite materials and the attachment of acrylic veneers via a composite or unfilled resin for the same purpose.
  • they may be used as adhesion promoters in the attachment of single unit pontics to the abutment teeth via a composite or unfilled resin.
  • adhesion promoters of the present invention may be used to promote the adhesion of composite materials as described above to metal substrates and in this connection can find application in the construction of crowns and bridges in which a polymeric material is bonded to the framework or substrate formed of a metal such as a chromium/cobalt alloy, a gold/copper alloy or the like.
  • the adhesion promoter of the invention may also be used to improve the adhesion of adhesive materials containing polymerizable ethylenically unsaturated material to substrates other than tooth material, for example metallic substrates formed of metals such as chromium/cobalt alloys, gold/copper alloys or the like.
  • Pentaerythritol triacrylate phosphate PETAP
  • the ether extract was dried over magnesium sulphate and the ether was then removed from the dried extraction under reduced pressure to give the title compound as a clear colourless viscous oil, the infra-red absorption spectrum of which shows absorption peaks at 2800-2560; 1730; 1640; 1620; 1270; 1190 and 1060 cm- 1.
  • pentaerythritol trimethacrylate phosphate (PETMAP) and dipentaerthyritol pentaacrylate phosphate (DPEPAP) were produced from pentaerythritol triacylate and dipentaerythritol pentaacrylate, respectively.
  • the two products had infra-red absorption spectra as shown in Table 1.
  • a sample of the PETMAP was converted to its sodium salt (Na PETMAP by reaction with sodium hydroxide.
  • Tooth enamel treated as above using a PETMAP-containing adhesion promotor showed an average adhesion of 7.6 MPa (for 8 samples), after storage in water at 37°C for three months.
  • Tests were also conducted to ascertain the degree of protection against micro leakage afforded by the use of the polymerisable phosphates.
  • Extracted human teeth were selected for the absence of caries and cracks, coated with nail varnish, and set into resin with the crown exposed.
  • Two diametrically opposed cavities approximately 3 mm in diameter and extending about 2 mm into the dentine, were prepared in each tooth using a high speed handpiece, then thoroughly cleaned and dried with a dental air/water syringe.
  • a cotton wool wad was used to apply a 1 % w/v solution of the polymerisable phosphate ester in absolute ethanol to one cavity tooth, and the solvent evaporated with compressed air.
  • Composite resin as described above was then placed in the cavity, held under pressure with a matrix strip while it hardened, and finally finished with a medium grit abrasive disc lubricated with petroleum jelly.
  • the second cavity in the tooth was similarly filled and finished, but without using the phosphate ester pretreatment.
  • a composite material was produced as disclosed in the example of GB-A-1401805 except that there was used as inert filler a synthetic hydroxy apatite having a particle size of less than 60 pm.
  • a sample of the composite material was made up and the transverse tensile strength thereof was measured.
  • the transverse tensile strength was about 35 Mpa but when employing one which had been coated by slurrying it with a 1 % w/v solution of PETMAP in ethanol and then removing the ethanol under reduced pressure, the transverse tensile strength was about 70 Mpa.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Dental Preparations (AREA)

Claims (11)

1. Monophosphates à plusieurs liaisons éthyléniques insaturées de la formule:
Figure imgb0008
et leurs sels, dans lesquels:
R est un radical hydrocarbyle aliphatique (qui peut être interrompu par un ou plusieurs atomes d'oxygène), ayant une valance de n+1 et contenant de 4 à 16 atomes de carbone,
R1 est un atome d'hydrogène ou d'halogène ou un radical cyano ou un groupe alcoyle contenant 1 à 3 atomes de carbone; et
n est un nombre entier supérieur ou égal à 3.
2. Composés selon la revendication 1, caractérisés en ce que n est un nombre entier égal à 3, 4, 5 ou 6.
3. Monophosphate-triacrylate de pentaérythritol.
4. Monophosphate-triméthacrylate de pentaérythritol.
5. Monophosphate-pentaacrylate de dipentaérythritol.
6. Monophosphate-pentaméthacrylate de dipentaérythritol.
7. Composition promoteur d'adhérence, convenant pour améliorer l'adhérence d'un produit d'obturation dentaire composite sur des dents naturelles, comportant une solution dans un solvant organique volatil d'un composé à plusieurs liaisons éthylèniques insaturées, caractérisée en ce que le composé à plusieurs liaisons éthylèniques insaturées est un monophosphate à plusieurs liaisons éthylèniques insaturées ou un sel de celui-ci, selon l'une quelconque des revendications 1 à 6.
8. Composition selon la revendication 7, caractérisé en ce que le solvant est un alcool aliphatique inférieur.
9. Composition selon la revendication 7 ou la revendication 8, caractérisé en ce que la solution contient de 0,5 à 10% en poids de phosphate polyinsaturé.
10. Produit d'obturation dentaire, contenant un produit polymérisable à liaisons éthyléniques insaturées, un initiateur pour la polymérisation, une charge inerte et un composé à plusieurs liaisons éthyléniques insaturées, caractérisé en ce que le composé à plusieurs liaisons éthyléniques insaturées est un monophosphate à plusieurs liaisons éthyléniques insaturées ou un sel de celui-ci, selon l'une quelconque des revendications 1 à 6.
11. Procédé pour faire adhérer une résine polymérisable par addition de radicaux libres sur un substrat, caractérisé en ce que le substrat est d'abord traité avec un monophosphate à plusieurs liaisons éthyléniques insaturées ou un sel de ce produit, selon l'une quelconque des revendications 1 à 6.
EP83300754A 1982-02-16 1983-02-15 Promoteurs d'adhésion Expired EP0088527B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8204511 1982-02-16
GB8204511 1982-02-16

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EP0088527A2 EP0088527A2 (fr) 1983-09-14
EP0088527A3 EP0088527A3 (en) 1984-07-18
EP0088527B1 true EP0088527B1 (fr) 1987-07-22

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EP (1) EP0088527B1 (fr)
CA (1) CA1198444A (fr)
DE (2) DE88527T1 (fr)

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US6245872B1 (en) 1998-02-17 2001-06-12 Espe Dental Ag Adhesive securing of dental filling materials

Also Published As

Publication number Publication date
CA1198444A (fr) 1985-12-24
DE3372574D1 (en) 1987-08-27
EP0088527A3 (en) 1984-07-18
EP0088527A2 (fr) 1983-09-14
DE88527T1 (de) 1984-01-05
US4514342A (en) 1985-04-30

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